Thermoplastic products derived from rubbers



Patented Sept. 18, 1945 THERMOPLASTIC raonucrs DERIVED FROM RUBBERS Thomas W. Bartram, Nitro, ,W. Va., assignor to I Monsanto Chemical Company, St. Louis, Mo., a

' corporation of Delaware No Drawing. Application June 11, 1942, Serial No. 446,608

18 Claims. (Cl. 260-768) This invention relates to new thermoplastic products derived from rubbers and to the preparation of the same,

In accordance with this invention a rubber is treated with an organic sulfophosphine halide. While useful products have been obtained by treating rubbers with organic phosphine halides, it has now been found that the sulfophosphines behave similarly. Accordingly, the organic suli'ophosphines can be substituted directly or with but slight modification in the process and compositions disclosed in vco-pending applications 01 George D, Martin, Serial Nos. 346,991, filed July 23, 1940; 364,598, filed November 6, 1940; 416,587, filed October 25, 1941, and 416,588, filed October 25, 1941, and in co-pending application of David J. Beaver, Serial No. 417,577, filed November 1,-

1941. Furthermore, the rubbery products obtained from a rubber and an aryl sulfophosphine halide in the presence of a suitable modifying agent as hereinafter described may be substituted for the rubber like products obtained from a rubber and an aryl phosphine halide in the compositions disclosed in co-pending application of haul M. Downey, Serial No. 426,069, filed January s, 1942.

While the organic constituent in the sulfophosphine halide may be selected from a wide variety of organic radicals, it is preferred to use a product in which a carbon atom of the organic group is linked directly to phosphorus. As typical examples of organic sulfophosphine halides which may be used to prepare the new products mention is made of the following but the invention is by no means limited thereto: phosphenyl sulfochloride, thiophen sulfodichlor phosphine, tolyl suliodichlor phosphine, 1,3,4 trimethylphenyl sulfodichlor phosphine, 1,3,5 trimethylphenyl sulfodichlor phosphine, xylyl suliodichlor phosphine, biphenyl sulfodichlor phosphine, alpha naphthyl sulfodichlor phosphine, tetrahydronaphthyl sulfodichlor phosphine, meta diphenylphenyl sulfodichlor phosphine, decyl ph'enyl sulfodichlor phosphine, diethyl amino phenyl suli'odichlor phosphine, dimethyl amino phenyl suliodichlor phosphine, tertiary butyl phenyl sul'fodichlor phosphine, ditolyi suli'ochlor phosphine, dixylyl sultochlor phosphine, tolyl sulfodibrom phosphine, alpha naphthyl sulfodibrom phosphine, benzyl sulfodichlor phosphine, phine, plienetyl sulfodichlor phosphine, meta andpara hydroxy phenyl sulfodichlor phosphine, chlorphenyl sulfodichlor phosphine, bromphenyl anisyl sulfodichlor .phossulfodichlor phosphine, ethyl phenyl sulfodichlor 56 amyl sulfodichlor phosphine, hexyl sulfodichlor phosphine, butyl sulfodichlorphosphine; amyl suliodibrom phosphine, diamyl sulfochlor phosphine, cymyl sulfodichlor phosphine, dicymyl sulfochlor phosphine, retyl sulfodichlor phosphine, retyl sulfodibrom phosphine, ethyl sultodichlor phosphine and equivalents and analogues thereof.

A convenient method of preparing the sulfo phosphine halides 01' this invention is to react the organic phosphine halide with sulfur although other methods may be used as for example the reaction of PSCh with a suitable hydrocarbon. However, the invention is not limited to the method of preparation. The aryl phosphine halides are usually made by reacting a suitable and hydrocarbon with a. phosphorus trihalide in the presence of anhydrous aluminum chloride (see 'Liebigs Annalen Vol. 212, p 206, 207). The reaction results in a composition comprising the aryl phosphine halide and aluminum chloride. This crude composition, preferably after the removal of unreacted hydrocarbon and phosphorus trihalide, combines readily with sulfur to produce a crude reaction mixture suitable for reacting directly with rubber. After heating liquid hydrocarbons as for example xylene, toluene or petroleum eth'er with a phosphorus trihalide in the presence of anhydrous aluminum chloride, there separates after completion of. the reaction, a top layer which consists essentially of unreacted hydrocarbon and phosphorus trihalide and a small amount of the reaction prodnot. The top layeris simply drawn off and reserved for future use. By increasing the proportion of catalyst the reaction can be brought nearer to completion so that eventually no layers separate. In either case the crude product still contains some unreacted ingredients and may be heated up to strip out these constituents.

The-following example illustrates in detail the preparation of a crude organic sulfophosphine halide but is not limitative oi the invention.

Substantially 255 parts by weight of stripped tolyl dichlor phosphine lower layer and 32 parts by weight .of sulfur .were charged into a glass or glass lined container of suitable capacity fitted the container was displaced by a stream of nitrogen and the mixture heated for about three hours at 130 C. The product comprising the desired tolyl sulfodichlor phosphine was reacted with rubber as described below.

Substantially 100 parts by weight of ground truck peels was heated with dry toluene to swell and soften the rubber and substantially 50 parts by weight of crude tolyl sulfodichlor phosphine dissolved in toluene added thereto with vigorous stirring. The reaction mixture was stirred at 55 to 60 C. for twenty hours and the toluene removed by distillation. Live steam was then introduced and after a thorough steaming 'out the product was washed with water, preferably on a mill having corrugated rolls or on other equipment adapted for washing tough plastic products. The washed product was dried to constant weight in an oven under vacuum. In this manner substantially 116 parts by weight of a hard resin was obtained,

In general the particular apparatus, the temperature and time of reaction can be widely varied. However, the ingredients must be brought into intimate and uniform association if it is expected to get reproducible results. To this end use of a solvent like benzene, toluene or carbon disulfide is of considerable benefit. However, a solvent may be dispensed -with by use of an efficient mixer. This may be of the Werner and Pfleiderer type or modifications thereof but in any case there should be little or no free space above the mixer blades. rubber further facilitates the reaction. Small amounts of water are usually present in rubber and since the amounts are more or less variable, it is desirable to remove the water before starting the reaction. A Banbury mixer or even an ordinary rubber mill may be used for carrying out the reaction but in the latter case it is necessary, where hard products are sought, to enclose the rolls and displace the moist air by a dry inert gas as for example carbon dioxide. Tight rolls and a small bank both aid the mixing. Once the reactants have been thoroughly mixed so that the mass is homogeneous throughout, the reactlon'mixture may be removed and heated in an ordinary oven to complete the reaction. While the nature of the reaction taking place is not known, the hydrocarbon content of the rubher is materially increased whereas the amount of halogen combined with the rubber is small.

The addition, during the course or the treatment of the rubber with the thio phosphine halide, of a suitable modifying agent, preferably aromatic polynuclear hydrwarbons, results in products possessing flexibility, elasticity and recovery, and other rubbery properties. Suitable modifying agents include phenanthrene, naphthalene, anthracene, retene, retene oil and rosin oil. In the case of retene a technical grade formed in the distillation of pine wood or rosin is entirely satisfactory and is preferred. A substantial proportion of the polynuclear hydrocarbon is found in the final products.

In a further example of the invention, again not limitative thereof, substantially 100 parts by weight of ground truck. peels was heated with dry toluene to swell and soften the rubber and substantially 50 parts by weight of crude tolyl sulfodichlor phosphine dissolved in toluene added thereto with vigorous stirring. The reaction mixturewas stirred at 55 to 60 C. for two hours, 80 parts by weight of technical retene added and the heating and stirring continued for eighteen hours. The toluene was then removed by distillation and the residue steamed out, washed, and dried all substantially as described in the foregoing example. 218 parts by weight of a tough rubbery product was obtained. In the presence of an organic accelerator and zinc oxide the product cured nicely with three percent sulfur. The vulcanizate possessed good resistance parations pure tolyl sulfodichlor phosphine was Use of well broken down i used. Tolyl dichlor phosphine was extracted from the crude reaction mixture by means of a suitable solvent, purified by distillation, and reacted with sulfur' as described above. The pure tolyl sulfodichlor phosphine was separated by distillation (b. p. 145.5" C. at 8 mm.) and the aforementioned rubbers treated therewith. The products were softer and more tacky than the product from ground truck peels and crude tolyl sulfodichlor phosphine. Somewhat tougher products can be obtained by the addition of anhydrous aluminum chloride to the sulfodichlor phosphine prior to the treatment with rubber.

Ground truck peels was heated with chlorphenyl sulfodichlor phosphine and technical retone to produce a rubbery product. The preparation was carried out substantia ly as described above substituting 50 parts by weight of chlorphenyl sulfodichlor phosphine (B. P. 125- 126 C. at '7 mm.) for the tolyl sulfodichlor phosphine to obtain 194 parts by weight of rubbery product. This product was vulcanized by heating in a press with 4 percent sulfur in the presence of an organic accelerator and zinc oxide, and strips or the vulcanizate were immersed in gasoline and benzene and found to possess good resistance to swelling,

As will be appreciated from the foregoing description and examples a wide variety of rubbers, both natural and synthetic, are applicable in the process of the present invention. Accordingly, the term fa rubber" is employed in the claims to define a vulcanizabie plastic material which possesses high extensibility under load coupled with the property of forcibly retracting to approximately its original size and shape after the load is removed. Typical rubbers which can be used in the invention include for example crude indie.

rubber, reclaimed rubber, ground scrap, balata, gutta percha, chlor butadiene polymers (Neo prene), butadiene polymers and copolymers in cluding such well known materials as Perbunan and Hycar OR which are copolymers of butadiene-1,3 and acrylic nitrile and Buna S, a copolymer of btadiene-l,3 and styrene, guayule, juletong .or pontionac and polymerized cashew nut oil.

Again this invention is not limited to the specific examples and compositions set forth to illustrate the invention. Other solvents and other organic sulfo phosphine halides can be used as .well as other means of efiecting the reactions. Again, the new products can be admixed with other plastic or resinous materials. This invention is limited solely by the claims attached hereto as part of the present specification.

What is claimed is:

l. A new composition of matter obtained by intimately mixing a substance selected from the group consisting of natural rubbers, polymers of butariiene-Lfi, copolymers of butadiene-1,3 and acrylonitrile, copolymers of butadiene-l,3 and styrene, chlor butadlene-1,3 polymers, scrap rubher and reclaimed rubber with substantially 50% by weight of an organic sulfo phosphine halide having halogen directly linked to the phosphorus atom and heating the mixture.

2. A new composition of matter obtained by in timately mixing a substance selected from the group consisting of natural rubbers, polymers of butadiene-Lli, copolymers of butadiene-L3 and acrylonitrile, copolymers of butadiene-l,3 and styrene, chlor butadiene-1,3 polymers, scrap rubher and reclaimedrubber with substantially 50% by weight of an aromatic sulfo phosphine halide having halogen directly linked to the phosphorus atom and heating the mixture.

3. A new composition of matter obtained by in timately mixing a substance selected from the group consisting of natural rubbers, polymers of butadiene-l,3, copolymers of butadiene-l,3 and acrylonitrile, copolymers of butadiene-1,3 and styrene, chlor butadiene-l,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of an aryl sulfo phosphine halide having halogen directly linked to the phosphorus atom and heating the mixture.

d. A new composition of matter obtained by intimately mixing a substance selected from the group consisting of. natural rubbers, polymers of butadiene-L3, copolymers of butadlene-1,3 and acrylonitrile, copolymers of butadiene-l,3 and styrene, chlor butadiene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of. an aryl sulfo phosphine chloride having chlorine directly linked to the phosphorus atom and heating the mixture.

5. A new composition of matter obtained by intimately mixing a substance selected from the group consisting of natural rubbers, polymers of butadiene-1,3, copolymers of butadiene-1,3 and acrylonitrile, copolymers of butadiene-l,3 and styrene, chlor butadiene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of an aryl sulfo phosphine chloride having chlorine directly linked to the phosphorus atom in the presence of retene in an amount exceeding that of the said sulfo phosphine chloride and heating the mixture.

6. A new composition of matter obtained by intimately mixing a substance selected from the group consisting of natural rubbers, polymers of butadiene-l,3, copolymers of butadiene-l,3 and acrylonitrile, copolymers of butadiene-1,3 and timately mixing scrap rubber with substantially by weight of crude chlor phenyl sulfo dichlor phosphine having two chlorine atoms directly linked to a phosphorus atom and containing aluminum chloride and with retene in an amount exceeding that of the said sull'o dichlor phosphine and heating the mixture. I

9. A new composition of matter obtained by intimately mixing natural rubber with substantially 50% by weight of an aryl sulfo phosphine chloride having chlorine directly linked to the phosphorus atom and heating the mixture.

10. The method of making a new composition of matter which comprises intimately mixing a substance selected from the. group consisting of natural rubbers, polymers of butadiene-l,3, copolymers of butadlene-l,3 and acrylonitrile, copolymers of butadlene-1,3 and styrene, chlor butadiene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight oi" an organic sulfo phosphine halide having halogen directly linked to the phosphorus atom and heat ing the mixture.

11. The method of making a new composition of matter which comprises intimately mixing a substance selected from the group consisting oi natural rubbers,. polymers of butadiene-L3, copolymers of butadiene-1,3 and acrylonitrile, co

polymers of butadiene-l,3 and styrene, chlor bu tadiene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of an aromatic sulio phosphine halide having halogen directly linked to the phosphorus atom and heating the mixture. I

12. I'he method of making a new composition of matter which comprises lntimawly mixing a substance selected from the group onsisting of natural rubbers, polymers of butadlene-L3, co polymers of butadiene-1,3 and acrylonitrlle, co polymers of butadiene-1,3 and styrene, chlor butadlene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of an aryl sulfo phosphine halide having halogen directly linked to the phosphorus atom and heating the mixture.

13. The method of making a new composition of matter which comprises intimately mixing a substance selected from the group consisting of natural rubbers, polymers of butadiene-l,3, co-

polymers of butadiene-l,3 and acrylonitrile, copolymers of butadiene-1,3 and styrene, chlor butadiene-l,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by'weight of an aryl sulfo phosphine chloride having chlorine directly linked to the phosphorus atom and heating the mixture.

styrene, chlor butadlene-1,3 polymers, scrap rubher and reclaimed rubber with substantially 50% byweight of a crude alkyl phenyl sulfo dichlor phosphine having two chlorine atoms directly linked to the phosphorus atom and containing aluminum chloride and with retene in an amount exceeding that of the said sulfo dichlor phosphine and heating the mixture. I

'7. A new composition of matter obtained by intimately mixing scrap rubber with substantially 50% by weight of crude tolyl sulfo dichlor phosphine having two chlorine atoms directly linked to a phosphorus atom and containing aluminum chloride and with retene in an amount exceeding that of the said sulfodichlor phosphine and heating the mixture.

8. A new composition of matter obtained by ini 14. The method of making a new composition of matter which comprises intimately mixing a substance selected from the group consisting of natural rubbers, polymers of butadlene-1,3, copolymers of butadiene-1,3 and acrylonitrlle, copolymers of butadiene-1,3 and styrene, chlor butad ene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of an aryl sulfo phosphine chloride having chlorine directly linked to the phosphorus atom in the presence of retene in an amount exceeding that Of the said sulfo phosphine chloride and heating the mixture.

15. The method of making a new composition of matter whichcomprises intimately mixing a substance selected from the group consisting of Q butadiene-1,3 polymers, scrap rubber and reclaimed rubber with substantially 50% by weight of acrude alkyl phenyl sulfo dichlor phosphine scrap rubberwith substantially 50% by weight.

01' crude tolyl sulio dichlor phosphine having two chlorine atoms directly. linked to a phosphorus atom and containing aluminum chloride and with retene in an amountexceeding that of the said sulfo dichlor phosphine and heating the mixture.

17. The method of making a new composition of matter which comprises intimately mixing scrap rubber with substantially 50% by weight of crude chlor phenyl sulio dlchlor phosphine having two chlorine atoms directly linked to a phosphorus atom and containing aluminum chloride and with retene in an amount exceeding that of the said sulto dichlor phosphine and heating the mixture.

18. The method 01 making a new composition of matter which comprises intimately mixing natural rubber with substantially. 50% by weight of an aryl suifo phosphine chloride having chlorine directly linked to the phosphorus atom and heating the mixture.

, THOMAS W. BARTRAM. 

